Process for breaking petroleum emulsions



Patented Oct. 16, 1951 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, Uniyersity City, and Bernhard .Ke se u. Webs e Groves, M a i np i Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware No Drawing. Application February 21, 1950,

. Serial No. 145,579

15 Claims.

The present application is concerned with an invention which is the breaking of petrolen n emulsions of the water-in-oil type by subjecting the emulsion to theaction of a demulsii ler includns hydrophile synthet P OdPQ SJ S i .h drc P i Synthetic pr uc s brine c y lk ation products of the acylation product obtained by reacting (a) a fusible, carboxyl-eontaining Xylenesoluble, water-insoluble, acid-catalyzed, lowstage phenol-aldehyderesin; said resin being d8.- rived by reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the onehand, and an aldehyde having not over 8 carbon atoms and reactive towards both components of the mixture on the other hand, the amount of salicylic acid employed in relation to the noncarboxylated phenol being sufficient to contribute at leastone salicylic acid radical per resin molecule; said resin being formed in the substantial absence of trifunctional phenols, and said phenol being of the formula inwhich R is a hydrocarbon radical having at least 4 and not more than 14 carbon atomsand substituted in the ;2-,4,-6- position; and (11') an acylation -susceptiblechemical compound in which theelements are composed exclusively of members selected from the class consisting of carbon; hydrogen, oxygen, nitrogen; and snlfur, and chlorine, with the proviso that the'molecular weight of" such second reactant shall not be over :radicals, such as compounds having a hydroxyl radical, an amino radical, an amido radical, a sulfonamide or derivative thereof, or acombination of such radicals or similarly reactive radicals. Such hydroxylated compounds may be composed of carbon, hydrogen and oxygen only or may additionally have some other element, such as nitrogen, sulfur, chlorine, etc. In fact, it is not necessary that oxygen be present, as in the case of an amine or ammonia. Stated another way,

such carboxyl may be reactive towards any compound having either a hydroxyl or an amino or nitrogen atom, or both, or other obvious equivalents.

This broad invention-is generic to at leastthree sub-genera. One sub-genus is concerned with acylation-susceptible compounds derived from a carbonyl-containing resin and a second reactant containing carbon, hydrogen and oxygen only.

A second sub-genus of thepresent invention is concerned with such instances where the acylation susceptible' compounds, either organic or inorganic, contain nitrogen.

A third sub-genus of the broad invention is concerned with certain products" of' acylationsusceptible organic compounds in which there is present at least one element other than carbon and hydrogen and either oxygen or nitrogen or both, said other element being selectedfrom the class consisting of sulfur and chlorine.

The method of preparation of all the compounds within the generic class is essentially the fusible,

scribed, and particularly an organic compound having a molecular Weight under 25,000. The result of suchacylation reaction, which' may be esterification or amidification, or both, is anacylation product or: intermediate.

The first step is-toobtain andprepare a' statue Having obtained such intermediate product by reaction with the carboxyl radical of the xylene soluble resin; the next step involves reaction with an alkylene oxide such as ethylene oxide, prohydrogen and oxygen. Where the reaction in:- voives a hydroxyl radical free from other interfering radicals as in the case of a monohydric alcohol, polyhydric alcohol, fractional. ester, or

pylene oxide, butylene oxide, giycide and methylthe like, one can employ any conventional proglycide. cedure, but the one referred to is a customary For all practical purposes such oxyalkylations esterincation reaction employing an acid cataare conducted in a conventional manner. The lyst. Other obvious equivalents suggest themoxyalkylated derivatives so obtained are emselves such as reaction with a polyhyclric alcohol ployed for the resolution of petroleum emulsions 19 followed by subsequent reaction with a high of the water-in-oil type. moial monocarboxy acid. lhere is'nothing to be These three sub-genera collectively do not ingained, however, by employing such added step. clude all varieties of acylation-susceptible comor OOnv ee, we h v used a eonvehtienelv pounds which are reactive towards carboxyltwo-piece laboratory resin pot. The cover part containing phenol-aldehyde resins of the present of the equipment had four openings: One for rekind. Examples of other classes of acylati-on-susflux condenser; one for the stirring device; one ceptible compounds are esters in which there is for a separatory funnel or other means of addpresent a polycarboxy acid, nitrogenous coming reactants; and a thermometer well. In the pounds obtained by treating oxyalkylated phenolm pu ation e p y the S p y fu e aldehyde resins with ethylene imine or propylene 20 insert for adding reactants was not used. The imine, and compounds comparable to those of the device was equipped with a combination reflux. present subgenus in which chlorine, for example, and Water-trap app 5 t the Single is replaced by bromine. piece of apparatus could be used as either are- The carboxyl-containing xylene-soluble resins fiu c enser 0 a W te p, depending on the which we use as intermediates for preparing the position of the three-way glass stopcock. This products used in accordance with the invention Permitted v e t W thd awal 'Of Water from are described in our application Serial No. 137,293, the Water trap- The q p furthermore, filed January 6, 1950, and reference is made to p mi a Setting of t e Va ve W ut diethat application for a complete and full descripconnecting the equipment. The resin pot was tion of these resins and to Examples 6a through heated With a glass fiber electrical heater- 00n- 24a thereof for specific examples of suitable resin structed o fit snu ly ar un the resin pct. Such 24a thereof for specific examples of suitable t With regu1at0rS,ere readily va ab e resins. The selected resin, either dissolved in xylene To produce products used in the practice of or h Xylene a d, was pla in the resin p the present invention, these resins are reacted along With the ecte y y ated reactant with acylation susceptible materials reactive and a Small amount-0f Catalyst. u ly parawith the carboxyl groups present in the resin. In toluene sulfonic acid. The mixture was refluxed describing suitable acylation-susceptible man stirred during t e nt pr dur terials, to illustrate the invention, we will first Wh n the p p r r p howe hat describe acylation with suitable compounds con- 40 the amount of water separated W s p taining only carbon, hydrogen and oxygen, then mately that expected from reaction the operaaoylation with compounds containing nitrogen, tion was stopped. The intermediate SO obtained then acylation with compounds containing chloof Cou dissolved in y e y e rine or sulfur, then describe the oxyalkylation of W e y removable by Vacuum distillation these intermediates and then describe the although for Subsequent e o With an y process of demulsifying using th oxyalkylated ene oxide there is no objection to its presence. r d t I The subsequent tables show the particular resin employed and the amount, the hydroxyl- COMPOUNDS CONTAINING CARBON, HYDROGEN ated reactant and amount the amount cata- AND XYGEN NLY lyst employed (para-toluene sulfonic acid) and amount, added solvent and amount, the ratio be- The intermediates are prepared by conventween available hydroxyls and carboxyls, the ap tie'nal acylation reactions p yi b xy proximate reflux temperature, time of refluxing, containing xylene-soluble resins described in our the amount of water evolved, and the appearance said application Serial No. 137,293 along with of thefinal product. The data are in essence hydroxylated reactants containing only carbon, self-explanatory.

R t H C Bf cfg b A t g of Amt. of at Esmera d as; at. 3;; 3;, set h s, assets solubility of Group ployedy Resin Grams yst, Gum's to C. hrs. c.c. Ester Vent Free Ester Grams rams droxyl 1b Carbowax 4000 mono- 418 711 85.5 5 90.1 1:1 170 4 5 7.7 Dk. brown Wtr.-dispersible stearate. tacky Solid. foam. 2!; Caaggggax 4000 mono- 418 711 85.5 5 96 1:1 174 4% 10.4 do Do. 3b Eglliylgneglycolmono- 85.2 711 228 5 160 1:1 168 4% 5.9 ....do Do. 45 Eghi leiieglycolmond 89.3 7:: 228 5 160 1:2 161 5% 9.8 do D0. 55 Giyiifitihono-oleate- 93.3 7a 228 5 197.7 1:2 153 5A 8.6 do Do. 6b Diethylene glycol 101 7a 228 5 157 1:1 162 4 7.1 Dk. brown soft. Wtr.-dispersible.

mono-ricmoleate. sol. I Glycerol mono-oleate 93 7a 228 5 152 1:1 162 4 7.8 do Do. Glyceryldioleate 162 7a. 228 5 160 1:1 162 4% 6.5 Dk. brown Sltly. water distacky sol. persible. 9b (lazggrvgti 4000 mono- 392 10a 75 5 67.0 1:1 174-182 6 10.4 .....d() Wtr.-dispersible 10b Ggrbox i000 mono- 392 10a 75 5 43.0 1:1 176182 6% 12.0 Dk.brownVisc. i

oleate. Liq.

1 Example number is that of S. N. 137,293.

now Patent 2,499,366, granted March 7, 1950, and

reference is made to that patent for the details or the procedure. 7

' Example 2m Grams Para-tertiary amyphenol (1.0 mole) 164 Formaldehyde 37% (1.0 mole) 81 HCl 1.5

Monoall yl (CC 20, principally ell-ca) benzene monosulfonic acid sodium salt 0.8 Xylene 100 The procedure followed was the same as that Example 3aa The phenol employed (164 grams) was a commercially available mixed amylphenol containing approximately 95 parts of para-tertiary amylphenol, and 5 parts of ortho-tertiary amylphenol. It was in the form of a fused solid. The procedure employed was the same as that used in Example laa, preceding. The appearance of the resin was substantiall the same as that of the product of Example 211a.

Sometimes resins produced from para-tertiary ampylphenol and formaldehyde in the presence of an acid catalyst show a slight insolubility in xylene; that is, while completely soluble in hot xylene to give a clear solution they give a turbid solution in cold xylene. Such turbidity or lack of solubility disappears on heating, or .on the addition of diethylethyleneglycol.

We have never noticed this characteristic property when using the commercial phenol of Example 3:10., which, as stated, is a mixture containing 95% para-tertiary ampylph'enol and 5% ortho-tertiary amylphenol. In fact, the addition of 5% to 8% of an ortho-substituted phenol, such as ortho-tertiary amylphenol to any difunctional phenol, such as the conventional parasubstituted phenols herein mentioned, usually gives an increase in solubility when the resulting resin is high melting, which is often the case when formaldehyde and an acid catalyst are employed.

Example 411a The phenol employed (178 grams) was paratertiary hexylphenol. This is a solid at ordinary temperatures. The procedure followed was the same as that used in Example laa, preceding, and the appearance of the resin was substantiall the same as that of the resin of Example 2aa.

The solvent-free resin is slightly opaque in appearance, reddish-amber in color, semi-hard to pliable in consistency, and xylene-soluble.

Example 5aa dish-amber in color, soft to pliable in consistency,

and xylene -soluble.

There area considerably greater numb-er of examples of this class of alkylphenol aldehyde resins known; but the foregoing few illustrate the intent sufiiciently. The phenols employed are difunctional in all cases, and have a hydrocarj bon 'substituent of from 8 to 14 carbon atoms,

located in the 2,4,6 position. The aldehydes all have 8 carbon atoms or less. The products are .all water-insoluble, xylene-soluble, fusible resins.

These resins are then converted inqto poly- 4 hydric alcohol reactants by reaction with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide, so as to convert the resin into a polyhydric alcohol. sense to difierentiate an-alkanol or an equivalent hydroxyl from a phenolic hydroxyl. Such resins having 3 or more phenolic hydroxyls can be treated with sufiicient'of the'alkylene oxide to convert the resin molecule into a polyhydric alcohol.

or ethylene oxide, per resin unit, and the upper limit might be moles of the alkylene oxide or even more, per phenolic hydroxyl. I

The procedure used is substantially the same as employed in converting such resins into surface-active emulsifiable, miscible, or soluble compounds. Reference is made to our co-pending application, Serial No. 8,722, -filed February 16, 1948 now Patent 2,499,365, granted March 7, 1950, for details of this oxyalkylation procedure. This oxyalkylation procedure is also described later in the present opplication. We have prepared hundreds of resins of the kind just described. We have subjected such resins to oxyalkylation on a scale varying from a few hundred grams in the laboratory to hundreds of pounds .on a plant scale.

The following examples illustrate. and describe the oxy-alkylated derivatives of such phenolaldehyde resins:

Example 1bb operated at a speed of approximately 250 R. P. M..

There were charged into the autoclave 1555 grams of a resin. of the kind identified by Example 1aa,preceding. This resin was dissolved in 1445 grams of solvent (xylene); 45 grams of sodium methylate were added. The autoclave was sealed, swept with nitrogen gas, and stirring started immediately and heat applied. The

temperature was allowed to rise to approximately 145-150 C. At this point the addition of ethylene oxide was started. It was added continuproduction of, first, an emulsifiable product and, finally, of a readily water-dispersible or soluble product. This is shown in the first 3 lines of the following table. 7

The other examples recited in the table represent still further examples of the preparation of this oxyalkylatedamylphenol-aldehyde class 5 of reactants.

Polyhydric alcohol is used in the usual The lower limit might be one or two moles of an alkylene oxide, for instance, glycidol The polyhydric reactant designated 63bb in the following table is the resin of Example 200a above oxyethylated with 1750 grams of ethylene oxide to 1760 grams of the resin with 2000 grams of xylene as solvent, grams of sodium methylate as catalyst, time one hour, maximum temperature 180 0., maximum pressure 100 lbs. per sq. in. It is water soluble.

Amt. Solvent Sod. Max. Denv- EtO Temp.

- Taken, Present, Methylate Time Pres., lbs. Solubility in t 01:115. (501- Gms. Adde g (hrs.) Mfg" per sq. Water vent Free) (Xylene) Gms. inch 100 1. 555 1, 445 45 425 150 00 Insoluble. v 150 1,157 848 1.350 14 188 95 Emulsifiable. 200 790 255 1.050 1A 170 so Water Soluble. laa 518 482 15 1,425 1A 183 100 Emulsifiable. lac 415 385 15 1,700 x 1110 120 Water Soluble. lau 353 633 15 2. 409 194 100 Do. 505 758 177 s00 54 101 100 Do. laa 223 1, s15 192 95 Do. laa 214 2, 039 4 171 90 Do. 141a 190 2, 050 171 so Do. 1110 205 2, 223 4 170 95 D0. 2410 1.575 400 )4 150 Insoluble. 1250 1,510 1,225 15s 80 Emulsifiable. 1300 1,787 975 4 173 00 Water Soluble. 1400 1, 490 550 as 150 150 Do. 1550 954 250 M 150 100 Do. 202 290 1, 742 171 95 Do. 2710 142 1, 778 y. 150 Do. 200 183 2, 445 205 100 Do. 2111; 20s 1, 571 1A 100 75 Do. 21m 212 2, 126 171 100 D0. 2cm 227 1, 993 194 Do. 5011 1,580 325 54 150 50 Insoluble. 2300 1,490 1,000 2 171 Emulsifiable. 2405 920 1,390 is 172 150 Soluble. 500 735 1, 500 94 190 120 Do. 51m. 490 1, 480 100 150 Do.

Having prepared hydroxylated reactants as just The polyhydric reactant designated 6400 in the described in Examples 100-2712b above, the carfollowing table is the resin of Example 501a above boxyl-containing resinous materials are then reoxyethylated with 1800 grams of ethylene oxide acted therewith to produce the 'acylation products to 1920 grams of resin with 2000 grams of xylene which are the intermediates of this invention. 30 as solvent, 46.5 grams of sodium methylate as The acylation products obtained from such catalyst, time 1%. hours, maximum temperature xyalkylated alkylph nolal hyde r sins by re- 182 0., maximum pressure lbs. per sq. in. action with a carboxyl-containing aldehyde-resin 11; is 501111019 in t are. Illustrated by the examples of the folmwmg The polyhydric reactant designated 6500 in the table- 1 h C t t 35 following table is a resin obtained following the ai b g 1 t 12 procedure of Example laa above, from technicals ows y er 6 car Oxy amtng r 1y pure nonyl phenol 660 grams, formaldehyde employed in each example, such resins being those 37% 243 grams, concentrated HCl 9 grams, monodescrlbed under the same number and letter desalk 1 (C C rmci all C C benz n m no ignations in application Serial No. 137,293. 40 y P y 12 14 e 6 sulfonic acid sodium salt 2.5 grams, and xylene 300 grams, which resin was oxy-ethylated with 1825 grams of ethylene oxide to 1975 grams of resin, with 2000 grams of xylene as solvent, 48 grams of sodium methylate as catalyst, time 1%.; hours, maximum temperature 181.5 0., maximum pressure 103 lbs. per sq. in. It is water soluble.

Catalyst Amt. Amt.

Ex. No (Para- Used Carbox- Used Solvent Ratio Ex. No. Gms. ylic Gms. (Xylene) 53 3533 COOH 3 6 Water out R Y t t (Solvent Resin 1 (Solvent Gms. Add) to OH me an Free) Free) Gms 6300 176 7a 107 337 7 1:1 150 to 170 4 Approx. theoretical. 6300 141 7a 171 354 7 2:1 150 to 170 4 Do. 6300 70. 4 7a 128 359. 6 7 3:1 150 to 170 4 Do. 6300 176 9a' 100 282 7 1:1 150 to 170 4 D0. 6300 141 9a 159. 6 295. 4 7 2:1 150 to 170 4 D0. 6300 70. 5 9a 119. 7 302. 3 7 3:1 150 to 170 4 D0. 6300 156. 5 1211 113. 5 312 7 1:1 150 to 170 4 Do, 6300 117 120- 170. 5 312. 5 7 2:1 150 to 170 4 D0. 6300 70. 5 1211 153. 5 262 7 3:1 150 to 170 4 Do. 6300 140. 8 112. 6 297. 6 7 1:1 150 to 170 4 Do. 6300 108 1141 173 309 7 2:1 150 to 170 4 D0. 6300 70. 5 11a 168. 5 272 7 3:1 150 to 170 4 D0. 6300 156. 6 8a 119. 5 311 7 1:1 150150 170 4 D0. 6300 117 8a 179. 5 314. 5 7 2:1 150 to 170 4 D0. 6300 70. 5 8a 161. 5 261. 8 7 3:1 150 to 170 4 Do. 6400 157. 5 7a 101 294. 5 7 1. 2:1 150 to 170 4 D0. 6400 131. 5 7a 171 328. 5 7 2. 4:1 150 to 170 4 D0. 6400 88 7a 161. 5 283. 5 7 3. 6:1 150 to 170 4 Do. 6400 197 9a 100 320 7 1:1 150 to 170 4 D0. 6400 157. 5 9a 159. 5 3,30 7 2:1 150 to 170 4 D0. 6400 105 9a 160 343 7 3:1 150 to 170 4 D0. 6400 175' 12a 113. 5 304. 5 7 1:1 150 to 170 4 D0. 6400 131 203 328 7 2:1 to 170 4 DO. 6400 87. 5 12a 170. 5 275 7 3:1 150 to 170 4 D0. 6500 181. 5 7a 95 285. 5 7 1:1 150 to 170 4 Do. 6500 148. 5 7av 287 7 2:1 150 to 4 Do. 6500 109 7a 171 270 7 3:1 150 to 170 4 D0. 6500 234 9a 114 301 7 1:1 150 to 170 4 Do. 6500 163 9a 159. 5 247. 5 7 2:1 150 to 170 4 D0.

1 Example number is that of S. N. 137,293.

,is, 3, 4, or 6 cc.

Still another class of esters are the esters derived from polyhydric alcohols and the carboxylcontaining phenol-aldehyde --resins described above.

Example 941) The particular resin employed was the one described under the heading of Example 7a of application Serial No. 137,293. The polyhydric al-f cohol employed was ethylene glycol. The amount of ethylene glycol used was 9.3 grams. The amount of carboxylic resin was 256 grams. The amount of para-toluene sulfonic acid was 5 grams. The amount of solvent (xylene) present was 292 grams. The reflux temperature varied from 150 C. to 1'70" C. The time of refluxing was 4 hours. The solvent-free product was clear, reddish amber, and soft to tacky inappearance.

The water evolved was separated in a phaseseparating trap as previously described. In a large numberof similar experiments we have taken particular pains to measure the amount of water evolved. This, however, is not particularly significant, especially where the amount of Water formed is simply a fraction of a mole, that We have found the figure is not significant for a number of reasons (a) sometimes some of the Water tends to hang up in the apparatus; (1)) sometimes the reactants em- "ployed, although not necessarily in the instant 12 ent invention are products of high molecular weight obtained in various ways as, for example, the oxyethylation or oxypropylation of heatstable carbohydrates, including mannitan, sorbitol, etc. For example, sucrose can be treated with an alkylene oxide (ethylene oxide or propyleneoxide) in a ratio of 100 moles of oxidefor each initial hydroxyl radical. 1 Thus the molecular weight of such polyhydric alcohols may vary from ethyleneglycol (62) to compounds' whose molecular weights are in the neighborhood of 25,000. v

We prefer that the hydroxylated reactant, employed herein to esterify the carboxyl containing phenol-aldehyde resin, have a molecular weight not exceeding 25,000. r

COMPOUNDS CONTAINING Nrrsocnri pound of specified character, as described below.

Nitrogen-containing compoundswhich are'reactive towardsthe carboxyl group can be divided into various classes as to their structure. Reactivity towards a carboxyl radical generally case, contain a trace of moisture or some other :20 means the p se ce n themof either an'amino volatile substance which comes over with the nltlflgen atom an a rnQ e q "water and the reading appears to be high; (0) al nt that is.. hy n attached t0 o y nsometimes some other reaction, such as etheri- The 11101 C. r qm ds include am fication, takes place. In this case the reaction moma. hy e rsamc 'mtroe n -'was conducted until apparently no more water Compounds Include es such as p y, secdue to an acylation reaction came over. We have ondary and e y ammes, Polyammes as W911 indicated this amount of water as being approxs ammesr amines .contalm a ol -im-ately theor'eticalwhich is in accordance with 128110215 0f the q al t and. amines Whlch results. The formation of the ester yields a prod- 0011mm 1a r c hydrogen atomlattached :uct havingdifierent physical characteristics, for 10 0 OXygen a d O e o o e r c e hyd instance, a higher molecular weight. It yields a atoms attached to nitrogem p poses Of product having different chemical characteristics convenience the nitrogen-containing compounds than the reaction mixture, for instance,'a saponiemployable as reactants here are divided into the fication number. Similarly, the acid value or following classes 2'. f p a hydroxyl value of the finished reaction mass is 43 Class 1.Compounds containing only 1 nitro- ..different from that of, the unreacted initial mixgen atom'per molecule, ..with at. least 1 reactive ture. hydrogen atom attached 'hereto but in the ab- The following table illustrates and describes sence of reactive hydroxyl groups. Ammonia and this and other ester intermediates. hydrazine are examples of inorganic compounds Amt. of Amt. of Ratio Reactant for ,Allltof v 11571;. Cajrgbn agiorli is fi g; a g Afiggi j gg (gollvenis g gf 3:5? Ti1r1ne AppearanceEoffi Solvent Free 0. W] 8.1 OXY y 939 o 111 T5. S 91' played, Resin 1 Grams, (P.T.S. to Hy- C. Group Grams Grams Grams droxyl 94b-.. Ethylene glycol- 9.3 7a 256 5 292 2=1 isg c to 4 Oltearlreddish aster sea to ac y. 7, 95b Propylene glycoL. 11.4 711 256 5 292 2:1 150 C. to 4 Clear, reddish amber soft to 170 C. semi-fluid. 96b..- Glycerol 13. 8 7a 256 5 292 2:1 150 C. to 4 Clear, reddish amber soft to 170 C. semi-pliable. 97b do 9.2 711- 256 5 292 3:1 ;);QSLQto 4 Reddish, black, hard brittle. 98b..- Diglycerol 44 7a- 211 5 259' 1:1 150 0.17 0 4 Reddish amber, semi-soft to 170 o. pliable. 99b.. 22 7a 213 5 261 2:1 150 C. to 4 Reddish black, hard and 7 170 0 brittle. 10%.. 17.6 711 257.4 5 294.6 3:1 150 C. to 4 Reddish amber, hardend C brittle. 1010-- Sorbltol 54.6 7a 268 5 299 1.04:1 9. m 4 Do.

0 10211-- do 27. 3 7a 266 5 300 2.08:1 150 3. w 4 Do.

. l03b do 18 7111 256 5 292 3:1 150 9. m 4' Do.

. 17o 104b Tetramethylol as 711. 25a 5 292 2:1 150 0. to 4 Do. 7

cyclohexanol. 170 C. 1051).- Propylene glycol 304 7a, 128 7 197 1:1 150 C. to 4 Dk. amber slightly opaque;

170 0 soft, fluid. V r p 1 Example number is that of S. N. 137,293.

* Para toluene sulfomc acid,

Further examples of acylation products which are included among the intermediates of the presof this class. Primary amines like ethylarnine, isopropylamine, butylarnme, amylamine, hexylamino, heptylamine, octylamine, decy-lamine,

tetradecylamine, hexadeoylam-ine, and octadecylamine are members of the class. High. molal primary amines, like those sold by Armour & Company, Chicago, as Armeens, usually with a figure designation showing the numbers of .C atoms in the alkylradical, e. g., Armeen "Armeen 12,." Armeen 16, etc.,are included.

So are secondary amines like diethyl'amin-e,

dipropylamine, di-butylamine, diamylamine, dihexylamine, dioctylami-ne, etc. Also included, are aniline, cyclohexylamine, bis-(dimethylbutyllamine, 1 3 dimethylbutylamine, 2- amy-l 4 methyl pentane. Amides are also included in this class, but are commonly not attractive for use here because of the difficulty of securing satisfactory reaction to produce secondary amides. Other useful amines of this class will be suggested by the above-recited list.

Class 2.Compounds containing only 1 nitrogen atom per molecule, but in which a hydroxyl group is the only reactive and functional group, as here. employed. In this class are. tertiary alkanolamines like diethylethanolamine, dimethylethanolamine, triethanolamine, diethylpropanolamine, methyldiethanolamine, ethyldipropanolamine, phenyldiethanolamine, etc. The products obtained by reacting such amines with alkylene oxides like ethylene oxide or propylene oxide are also useful, e. g., triethanolamine may be reacted with ethyleneor propylene oxide. Alkyl primary amines, particularly those in which the alkyl grouporiginates in fatty materials and contains from about 10 to about 18 carbon atoms, may be treated with such alkylene oxides to produce useful nitrogen compounds of the generic formula, R-di(AlkO)nH-N. Similarly, amides of the generic formula RCONHz, may be oxyalkylated to produce compounds of the generic formula,

(A k MH RC ON (A1kO),.H'

The ricinoleyl amides of dialkylamines are also examples of this class. Other examples of similarly useful reactants of this class will be suggested by the above list.

Class 3.--Compounds containing only 1 nitro- :gen atom per molecule and having, in addition to :at least 1 reactive hydrogen atom attached thereto, also at least 1 reactive hydroxyl group. In this class are included monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, ethylethanolamine, propylethanolami'ne, ethylpropanolamine, phenylethanolamine, 2- amino-2methyl-l-propanol, 4-amino-4-methyl- 2 pentanol, 4 amino 2 butanol 1 dimethylamino-Z-propanol, 5-isopropylamino-l-pentanol, etc. The high-molal monocarboxy acid amides of monoalkanolamines are also examples of this class. Obvious equivalents will be suggested by the above list.

Class 4.Esters of tertiary alkanolamines having only 1 nitrogen atom per molecule, to which nitrogen atom there are attached no reactive hydrogen atoms, but in'which ester molecule there is at least 1 reactive hydroxyl radical, either attached to the nitrogen atom through a suitable divalent radical or else as a part of the. acyl radical present in said ester. The acyl radicals are those found in monocarboxy acids having 8- C atoms' or more. Examples of this class of nitrogen compound are the esters produced from oleic acid; and ethyldiethanolamine or from ricin- 14 oleic acid and diethylethanolamine. In the case of the above oleic esters, esterification consumes onl one of the two hydroxyl groups originally presentin that alkanolamine, leaving one such reactive hydroxyl group in the ester, for use for the present purpose. In the case of the ricinoleic ester above, esterification consumes the only hydroxyl group originally present in the alkanolamine there used; but the ricinoleic radical itself contains a reactive hydroxyl group, and the ester is therefore still reactive for the present purpose. In preparing the compounds of this kind, there may be employed only as many acyl radicals as there are alkanol radicals, less one; except that, if the acyl radical itself retains at least .one reactive hydroxyl group after esterification, then one ma use as many acyl radicals as there are alkanols radicals. Examples of suitable alkanolamines have already been recited under Class 2 above; but some of the examples there recited will not serve here in all cases because they contain only one reactive hydroxyl group and this is destroyed in esterification. If ricinoleic acid is the acylating reactant, all those recited there are useful here. It is apparent from the foregoing description that the intent is to retain at least one reactive hydroxyl group in the ester prepared from the tertiary alkanolamine and the acylating reactant employed.

Class 5.-Compounds which are non-resinous,

which contain more than 1 nitrogen atom per molecule, and which contain no acyl group. Examples include the alkylene polyamines like ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, dipropylenetriamine, etc. These a1- kylene polyamines may be treated with an alkylene oxide like ethylene oxide or propylene oxide to produce derivatives which are also useful here, such as hydroxyethylethylenediamine, tetraethanoltetraethylenepentamine, etc. Oxyalkylation may be continued, of course, until a considerable number of alkyleneoxy groups have been introduced, Without adversely affecting the utility of such derivatives here. Imidazolines, both monoimidazolines and di-imidazolines, are included in this present class. Such compounds may be prepared by reacting, under sufiiciently severe conditions, a monocarboxylated acid and an alkylenepolyamine. For example, when oleic acid and tetraethylenepentamine are reacted in molar proportions at a temperature somewhat exceeding 200 C. amidification first occurs, with the elimination of 1 mole of water. On continued heating, especially at temperatures approaching 300 C., a second molecule of water is split out, the acyl group becomes an alkyl group, the imidazoline ring is formed, and the product is the monooleyl imidazoline of tetraethyle'nepentamine. If the proportion of fatty acid is doubled, a dioleyl imidazoline is produced, instead, Examples of such monoand di-imidazolines are recited and described in U. S. Patents Nos. 2,466,517 and 2,468,163, dated April 5, 1949, and April 26, 1949, respectively, to Blair and Gross. Furthermore, U. S. Patent No. 2,369,818, dated February 20, 1945, to DeGroote and Keiser, illustrates the fact that such imidazolines may be subjected to reaction with an alkylene oxide like ethylene oxide, to produce oxyalkylated derivatives thereof which are useful here.

Other examples of suitable reactants of the present class include 3-diethylaminopropylamine, 1-3-diaminobutane, triglycoldiamine, and the compound, NH2 CH2 3O (CH2) s0 (CH2) aNHz. See

amples of suitable nitrogen compounds of this class.

Class 6.-Compounds containing more than 1 basic nitrogen atom per molecule, and which also contain at least one high molal acyl group. The amides produced from monocarboxy acids like the fatty acids and alkylene polyamines like tetraethylenepentamine, and referred to in Class 5 above as being intermediates formed in the preparation of certain imidazolines, are representative of this class, For example, if one reacts 1 mole of oleic acidwith 1 mole of tetraethylenepentamine until 1 mole of water of reaction is removed, the product is an amide of the present class. Stearic acid or tall oil or other detergentforming acid having at least 8 C atoms maybe substituted for oleic acid in producing such an amide, with equally satisfactory results. Other alkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc., may be substituted for tetraethylenepentamine in the examples just discussed, to produce desirable amides. Or such polyamine may be oxyalkylated prior to use in the amidification reaction, using ethylene oxide or propylene oxide. If imidazolines of the kind included in Class 5, immediately above, are acylated, such acylated imidazolines are then properly included in the present class of nitrogen compounds. Other useful examples of nitrogen compounds of the present class are described in U. S. Patent No. 2,243,329, dated May 27, 1940, to De Groote and Blair.

Of all the members of this sixth class of nitrogen compounds, we prefer to employ as reactants here a type of product which is related to the esters of Class 4 above. If, instead of using molal proportions of high molal monocarboxy acidhaving 8 carbon atoms or more and of tertiary alkanolamine, as in the preparation of materials of Class 4, above, one employs 2 or more moles of alkanolamine for every mole of monocarboxy acid, desirable reactants of the present class are formed. These may be termed acylated polyaminoalcohols. To describe more precisely this particular and preferred type of Class 6 nitrogen compound, the following statement is made:

The compounds are acylated derivatives of a basic polyaminoalcohol of the formula:

said acylated derivatives thereof being such that there is at least one occurrence of the radical RCO, which is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R is a member of the class consisting of aminoalkanol radicals, and polyaminoalkanol radicals, in which polyaminoalkanol radicals the amino nitrogen atoms are united by divalent radicals selected from the class consisting of alkylene radicals, alkyleneoxyalkylene radicals, hydroxyalkylene radicals, and hydroxyalkyleneoxyalkylene radicals, and all remaining amino nitrogen valences are satisfied by hydroxyalkyl radicals, including those in which the carbon atom chain is interrupted at least once by an .OXygen atom; R is an .alkylene radical having at least 2 and not more than 10 carbon atoms n,

is a small whole number varying from 1 to 10; and RC0 i a substituent for a hydroxyl hydrogen atom.

In the foregoing formula, R may, in some of its multiple occurrences in the molecule, represent the same alkylene radical or it may represent different alkylene radicals, so long as each R contains from 2 to 10 carbon atoms. For example, oxyethylated, oxypropylated triethanolamine would contain some R radicals whichare C2H4 radicals, and others which are C3H'1 radicals.

Further description of this acylated polyaminoalcohol reactant will be found, for example, in U. S. Patent No. 2,470,829, dated May 24, 1949, to Monson. As a specific example of this preferred class of nitrogen compound, a passage from said Monson patent will be recited later below, in this application.

It is to be understood that isomeric forms of the nitrogenous compounds of all 6 classes above may be employed insteadof the forms referred to above, without departing from the invention.

The acylation products which constitute the intermediates here described are prepared by reacting a member of the class of carboxyl-containing, xylene-soluble, water-insoluble, acidcatalyzed, low-stage, phenol-aldehyde resins with a member of one of the classes of nitrogen compounds just recited above. In the more specific embodiment of this part of our invention, or what might be called its sub-generic aspect, reaction is effected between a resin of such class and a member of one group in Class 6 of said classes of nitrogen compounds. Both aspects are considered below.

Althoughthe reactions involved here may be ammonolysis, esterification, or amidification reactions, they all involve the introduction, into the nitrogen compound, of an organic acyl radical; hence the reactions are all properly termed acylation reactions, and the products are acylation products.

The following examples will illustrate this acylation reaction and preparation of such acylated intermediates.

For convenience, we have used a conventional two-piece laboratory resin pot. The cover part of the equipment had four openings; One for reflux condenser; one for stirring device; one for a separatory funnel or other means of adding reactants; and a thermometer well. In the manipulation employed, the separatory funnel insert for adding reactants was not used. The device was equipped with a combination reflux and watertrap apparatus so that thesingle piece of apparatus could be used as either a reflux condenser or a Water trap, depending on the position of the three-way glass stopcock. This permitted convenient withdrawal of water from the water trap. The equipment, furthermore, permitted any setting of the valve without disconnecting the equipment. The resin pot was heated with a glass fiber electrical heater constructed to fit snugly around the resin pot. Such heaters, with regulators, are readily available.

The selected carboxyl-containing resin, either dissolved inxylene or with xylene added, was placed in the resin pot, along with the appropriate other reactant. In the event that the other reactant was non-basic, such as a hydroxylated amide, a small amount of catalyst, usually paratoluene sulfonic acid, was added. When the other reactant was basic, as in the case of triethanolamine, usually no catalyst was added. The mix- 1'7 ture was: refluxed and stirred during the entire procedure.

\ When the phase-separating trap showed that the amount of water separated was approximately 18 Example 131b One mole of taraethmenebeatamme wa s exyalkylated with ethylene oxide until 7 moles there that expected from the reaction, the operation was 6 f beefl h' er fi using P ,FpnYF Q stopped. The intermediate so obtained was, of procedure ampe b z- TP SJPPQFF W 9 course, dissolved in xylene. The xylene was Sumd gm e et f .1650 readily removable by vacuum distillation al:- and 'p yee 2 !R though for subsequent reaction with an k n was then esterified with 1 nole of ricinoleic acid, oxide there is no objection to its presence. The uging no catalyst and gi ggie g followin exam le's illustrate the rocess: 2 hours .18 mg 0 .9

g p p water of esterification, in that time Thi s esterl E -am 10 1; fication product was then acylate'd by react-f ihg it with acarboxyl-containing phenol-alde The carboxyl containing resin of Example "7a of 15 hyd resin, as follows: Use 1'77 grams of the application Serial -No-. 137,293, in which the ratio prepared acylation product and 189' grams of of amyl phenol to salicyclic acid in the original the resin of Example 7a ofapplication Serial No; reaction mass was 4:1, was mixed (223 grams) 137,293, plus 234 grams of xylene. No catalyst with 38.9 grams of commercial triethanolamine was required, TheTeactioh mass was refluxed and 222 grams or xylene. In this mixture the with stirring for a t'o't'a'l o f Bhours, thetem'pera ratio of COOH radicalto amine waslz-l. Ac'atatur'e being 150 C'., during which time a the, lyst, para-toluene sul'fonic acid (5 grams), was retical amount of water was distilled cu. The added and the mass was refluxed at approxixylene-free product was a dark-brown, brittle mately 145" 'C., in a conventional glass laboratory solid, resin pot assembly, just described. After ap- Example v132b proximately '7 hours, the theoretical volume of a water had been collected and the operation was O el 111,016-01? hy e e remm nd 0- stopped. The product, which was a dark-brown Of all 011 was reacted t rqd aea d brittle solid, somewhat"water-dispersible, was the the t o m .c d tedfi er e t e i]. ester of the carboxyl-containing resin. U s, w h the temperature at 200? Q fgr 5.5 In similar fashion, several 'carboxyl-containing ho s and finally at 24 02 for l -5 hpll s- I A resins of the kind above described were reacted 0?- 1 gi wa er was; dlstllled ofi and; col with nitrogen compounds of the various classes 18011961; l lf s l The mide sp producedwas just recited, to produce the desired acylati'on E Y h th 5 1} Q P l-q Of ppl qar products or intermediates. These examples are 0 Sr al"N9.-13? 93,,using 149 grams oi amide, not set out here in the detail accorded Example 3 285 grams f r 288 gramexykn no cata; I066 above but are condensed into the following y The perature was held at 150 for 8 table. It is to be understood that the procedure rs Of ea stirring, nd refluxing the is in general that of Example 10Gb. Details of water of reaction being distilled off, The'resulteach of such preparations, including the nature s acy p t a a dark-brown. brittle of the resinand thexnitrogen body employed, the solid. amount of each, the amount of xylene present, Example 1331, the amount of catalyst (para-toluene sulfonic v p H acid) employed, if any, the molal ratio of car- An amide was pr p fied fQm talloiland tetraboxylradical, GOOH, tonitrogen body, the temyl pent m 1n usin 0.5 mo1. ,o f -each; re peratureof the reaction mass during processing, ac After a'fimg gh fs a1? 2 Q- Q the time of processing, the amount of water 10 ml. of water haddistilled The amide was evolved, are all set out in the table. The product acylaited S g ar oxy -c tainine resin i was in all cases a dark-brown, brittle solid; In Example appl cation SerialNo. 13' 93. all instances except in Example 1251), it was water- TO dQ th use 2 g a s 9fh? a de jllst predispersible, 5O pared, 214 grams of the carboxyl-contai'ning Oarbox Ratio Ex Amt. Amt. Xylene Catalyst. Tem TllIl Wt No Rig; (g) Nltrogeucompound (g) (g) l se (euer D-.- 7a 228 Triethanolamine.;- 38,5 121 1'45- 7 Theory 1070- 7a 228 Diethanolamine. 27.4 1:1 147' 7 Do. 1085.. 7a 228 Dipropanolamine 34.7 1 :1 152 7'-' Do. 10%.; 9a 200 Diethylenetnammc 25.2 1:1 7 Do. 11Gb" 9a 200 Armeen 10 45.3 151 5 Do. 1111)-. 9a 200 Armeen l2d.. 46.8 a 1 1 150 6 Do.- l'12b. 9a 200 Armeen l6d. 61.7 1:1 150' 5 Do. 1l3b.. 9a 200 ArmeenHflD 66.6 1:1 150' 5 D6. 1141).. 9a 200 Armeen 18D 67.6 121 150 5' a Do. 11%.. 9a 200 Armeen CD (Coco). 50.5 121 150 5- Do. 1165;. 9c 2510' Isopropahblamine... 18,4 1:1 145 5 D0. 117b.. 9a 200 Hydroxyethyl-ethylene am 25.5 1:71 147- 6' Do. 1180.- 9a 200 Dipropylenetriamineu. 32.1 1:1- 147 5, D0. 11%.. 9a 200 2-amino-2-methyl-l-propanol. 2118' 1:1 149" 5 'D'o. I20b- 9a 00 Diethanolamine 25.3 i=1 152 a nu. 121%. 9a 200 Armeen TC 107 1:1 152- 6 Do; 1220.. 9a 200 128 1:1 152 6 Do; 1 30 9a 2 o 31.8 mm r47 6% Do; 1241). 9a 200 2-amino-4-methyl-pentane 24.7 1:1 145 e o. 12%.. 9a 200 n-Decyla-mina--. 38.5 1:1 145 6 '0'; 1261);. 7a 428 "Dimethyletha'nolamine' 44.5 1 :1 150 8 Do 1272).. 9a 450 50 1:1 150 8 Do. 1286.- 9a 39.5 1:1 150 53, Do; 1290.. 8a 30.2 1:1 150 a Do. mom. 11a 30.8 15 1 150 eno.

Y Example number is'that of S. N. 137,293.

NOTE: The Armee'ns-are high-molal primary amines prepared in most cases from fattymaterials', and areeupiiliti 'ihniFcill'y Armour & 00., Chicago. See-their catalog entitled Armeens" for further description ofthem.

Example 134b 'Prepare the mono-ester of tall oil and triethanolamine by heating 1 mole of each at 240- 250 C. for 1.5 hours. Mix 125 grams of said ester, 219 grams of the carboxyl-containing phenolaldehyde resin of Example 9a of application Serial No. 137,293, and 255 grams xylene in the conventional resin pot, adding no catalyst. Reflux with stirring, at 150 C., for 8 hours, distilling off the water of reaction. The resulting acylation product, xylene-free, is a red-brown, brittle solid.

' Example 13527 Prepare the reaction product of ricinoleic acid and diethylethanolamine by employing molal proportions of these reactants, and heating at 240 -250 C. for 1.5 hours. The resulting product still retains the OH group in the ricinoleic acid residue present. React this product with the carboxyl-containing phenol-aldehyde resin of of Example 9a of application Serial No. 137,293 by refluxing, with stirring, 117 grams of the amine product, 224 grams of the resin, 259 grams xylene, withouta catalyst, for 8 hours, distillin on the water of reaction. The product, xylene-free, is a red-brown, brittle solid.

Example 13Gb Prepare an oxyethylated product from triethanolamine by introducing 3 moles of ethylene oxide per mole of triethanolamine, in conven- Example 137D Oxypropylate triethanolamine, using 3.46 molesof propylene oxide per mole of triethanolamine, inthe conventional oxyalkylation procedure described above, no catalyst being required. Time required was 8 hours, maximum temperature, 165 C., maximum pressure, 200 p. s. i. React 102 grams of this product with 233 grams of the carboxyl-containing phenol-aldehyde resin of Example 9a of application Serial No. 137,293, in the presence of 265 grams xylene, but no catalyst. After 8 hours-of stirring and refluxin at 150 C., distill on the water of reaction. The product, solvent-free, is a dark-brown, brittle solid. v

. Example 138D Oxyalkylate 1 mole of triethanolamine, using 3.46 moles of propylene oxide as in Example 13% above, the reaction requiring 8 hours at a maximum temperature of 165 C. and a maximum pressure of 200 p. s. i., and subsequently introducing 2.97 moles ethylene oxide into saidoxypropylated amine, in 30 minutes, maximum temperature 160 p. s. i. Thereafter, react the oxyalkylated amine, 130 grams, with the carboxyl-containing phenolaldehyde resin of Example 9a of application Serial No. 137,293,- 216 grams, xylene, 254' grams,- but no catalyst. Stir and reflux 8 hours at 150 C., distilling off the water of reaction. The prod I not, solvent-free, is a-red-brown, brittle solid.

Example 139!) React 0.5 mole of stearic acid and 0.5 mole of tetraethylenepentamine for 4.75 hours at 240 C., recovering 9 ml. water in the operation. React 190 grams ofthe amino product with 426 grams of the carboxyl-containing phenol-aldehyde resin of Example 120. of application Serial No. 137,293, adding 474 grams xylene, but no catalyst to the mixture. Stir and reflux 8 hours, distillin'goff the water of reaction. The solvent-free productis a dark-brown, brittle solid.

In preparing acylation product intermediates from a nitrogen body selected from Classes 1 to 6 above, and a carboxyl-containing phenol-aldehyde resin, we prefer to employ a nitrogen body selected from that sub-group of Class 6 which are acylated derivativesof basic polyaminoalcohols. This particular sub-group of nitrogen compounds which are included in the above-described- Class 6 are esters of tertiary alkanolamines having more than 1 nitrogen atom per' molecule. They have also at least 1 acyl group per molecule said acyl group being a higher molal group, hav

ing at least 8 C atoms. Their molecule contains: at least 1 reactive hydroxyl radical, either attached to nitrogen through a suitable divalent radical or else as a part of the acyl radical.

These nitrogen-containing esters are not to be confused with a closely allied group classified in Class 4 above; they differ in bein poly-amino, inthe present case, whereas said Class 4 compounds are all mono-amino.

The presently employed nitrogenous esters may most conveniently :be produced by reaction between a detergent-forming mono-carboxy acid having from 8 to 32 carbon atoms, or its glyceride or other ester, and a tertiary alkanolamine. For example, oleic acid and triethanolamine react to produce a very desirable example of the present class of nitrogen body. In such reaction, there must be present at least 2 moles of the tertiary alkanolamine for each acyl radical present, else the product is atleast in ...part. a mono-amine of Class 4, as above stated.

Usually, the acyl-containingjreactant used to prepare the present acylated polyaminoalcohol does not itself contain a hydroxyl group. In such cases, reaction must be effected between such non-hydroxylated-acyl-containing reactant and a tertiary alkanolamine containing at least 2 reacylated intermediate from which our final oxyalkylated product is to be derived.

To illustrate this: If ethyldiethanolamine, is

etherized by heating to a temperature sufficiently high to drive ofi a mole of water from 2 moles of the amine, the resulting Polyamine contains 2 I reactive hydroxyl'groups, the other two having been destroyed in the etherization process. If one of the remaining two hydroxyl groups is esterified with oleic acid, there remains in the final product one OH group suitable fOr com-- C., maximum pressure bination. with the COOH group of the carboxylcontaining resin reactant. Such an acylated polyaminoalcohol therefore qualifies here.

However, if etherization had been efiected between one mole of ethyldiethanolamine and one mole of diethylethanolamine, two of the three OH groups originally present would have been consumed. Th third OH group would be, consumed in the esterification of the oleic acid; and there would have been no residual OH group or groups available for reaction with the carboxyl-containi'ng resin reactant. In such case, use of ricinoleic acid instead of oleic acid would have resulted in an acceptable final polyamino product, since the acyl group of ricinoleic acid itself contains a reactive hydroxyl group and this would have been available for reaction of the. acylated polyaminoalcohol with the carboxyl-containing resin.

Therefore, in preparing acylated polyaminoalcohols of the desired class, one must bear in mind that such product must in all cases retain at least one OH group capable of reactingwith the COOH group of the carboxyl-containing resin. In other words, if the basic polyaminoalcohol, before acylation, he represented by the formula wherein R. is usually selected from the class of ethylene, propylene, butylene, hydroxypropylene, and hydroxybutylene radicals, and R is, in at least one instance, a nitrogen-containing radical, then at least one R radical must contain an OH group, so that there are present in said polyaminoalcohol, before its acylation, at least 2 reactive OH groups; and, after acylation, it will still retain at least one OH group. Different occurrences of R in a single molecule may, of course, represent different alkylene radicals or they may represent the same alkylene radical.

Oxyalkylation of the alkylene poiyamines, to introduce OH groups thereinto, produces polyaminoalcohols suitable for acylation here. As above stated, such oxyalkylated alkylene polyamines must contain a minimum, of two OH groups before acylation with the high molal detergent-forming monocarboxy acid or equivalent, so that a minimum of one OH is found in, the finally prepared acylated nitrogen body; unless said detergent-forming acids acyl group itself contains one or more OH groups, as in the case of 'ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, etc.

' The preparation of suitable acylated polyaminoalcohols is not novel with us here. It has been disclosed in numerous patents, including the following: U. S. Patents Nos. 2,324,488 and 2,324,490, both dated July 20, 1943, to De, Groote and Keiser; 2,259,704, dated October 21, I941, to Morison and Anderson; 2,306,329, dated Decembe'r22, 1942, to De Groote, Keiser and Blair.

Examples of the preparation of acylatedpolyaminoalcohols include the following:

'One mole of. ricinoleic acid is heated with 3 moles of triethanolamine at approximately 250 Qfor 6 hours. The product is an acylated. polyaminoaleohol.

One mole of castor oil is substituted for ricinoleic. acid. and 9 moles of triethanolamine are employed instead of r 3, above. The. product closely resembles that. of the first example above.

'Oleic acid may be substituted for ricinoleic acid or castor oil. Tall oil, which is principally ated polyaminoalcohol for the present purpose,

the following is given, substantially as it appears in U. S. Patent 2,470,829, dated May 24, 1949, to

Monson: A mixture of diamino and triamino materials is prepared (by heating triethanolamine) which correspond essentially to the two following type forms:

0HC2H4 noznlo ognm OHOQH CZH4OH canon 021140 clHlN Q2H4 OH After determining the average molecular weight of such mixture, it is combined with castor oil in the proportion of 1 pound mole of castor oil for 3 pound moles of the mixed amines, pound mole in the latter case being calculated on the average molecular weight, as determined. Such mixture is heated to approximately 160-260 C. for approximately 6 to 25 hours, until reactionis complete, as indicated by the disappearance of all of the triricinolein present in the castor oil.

Example 1 4 0b- Prepare a polyamino product from 925 grams of castor oil and 1090 grams triethanolamine, by heating at least 2 hours at a temperature of 250 C., and preferably 6 hours or even longer. The product contains approximately 2.5 triethanolamine residues per ricinoleio residue. Use 137 grams of it, 213 grams of the carboxyl-containing phenol-aldehyde resin of Example 19av of application Serial No. 137,293, and 250 grams xylene, but no catalyst, to produce an acylation product of said amino material. Reaction is conducted by stirring with reflux for 8 hours at 150 C. and distilling off the water of reaction. The product is a dark-brown, brittle solid.

Example 141 b Produce a derivative of triethanolamine by reacting 885 grams soybean oil with 1090 grams triethanolamine for 6 hours at 250 C. React 137 grams of the product with 209 grams of the carboxyl-containing phenol-aldehyde resin of Example 20a of application Serial No. 137,293, adding 254 grams xylene but no catalyst in the reaction, Reflux and stir 8 hours at 150 (2., distilling off the water of reaction. The prodnot, when solvent-free, is a dark-brown, brittle solid.

Example 142?) React 900 grams of tall oil with 2,180 grams of triethanolamine for 6 hours at 250 C. Thereafter mix grams of this product with 112 grams of the carboxyl-containing phenol-aldehyde resin of Example 9a of application Serial No. 137,293, and 348 grams xylene, but no catalyst. Reflux the mixture, with stirring, for 8 hours, distilling off the water of reaction. The product was not freed of solvent; but was used in xylene solution in the preparation of oxyalkylated derivatives, as noted below.

chlorohydrin.

- In the preparation" of; acylatedjintermediates from nitrogen containing acylation-susceptible;

Cdll/IPOUNDS CONTAI ING CHLORIMNE on SfJLFUR These intermediates are those in which a carboxyl-containing phenol-aldehyde resin "--is reacted with an organic acylation+susceptib1e reactant which contains chlorine or sulfur atoms- In addition to 'carbo'n or-- both in its molecule. and hydrogen, oxygen and nitrogen, or bothfmay be present in such reactant.

Examples of chlorine-containing acylationsusceptible reactants usable'here include chlorinated lower glycerides, like dichloromonostearin or dichlorodistearin, produced by the chlorination of oleic acid to form dichlorostearic acid, and the subsequent reaction thereof with an excess of glycerol. If desired, the dichlorostearic acid may be esterified in molar proportions with a polyhydric alcohol to produce a fractional ester containing chlorine; .or such halogenated acidmay be reacted with an alkylene oxide like ethylene oxide to produce such a fractional ester;

'Cardanol is a substituted phenol derived from cashew nutshell oil, and contains an'ethylenic side chain having 14 carbon atoms or more. It maybe subjected to mild chlorinatiom'to' introduce chlorine into such unsaturated side chain; See U. S. Patent No. 2,368,709, dated February 6; 1945;toHarvey. To produce a suitable'acylationsusceptible reactant from such chlorinated cardanol, one may subject, it to oxyalkylation; or'jone may'form a phenol-aldehyde resin from said chlorinated cardanol and an aldehyde like formaldehyde, and subsequently oxyalkylate'said' resin. Either oxyalkylated derivativeds usable here." See our co-pending'application, Seria'lfNo. 8,722, filed 7 February 16, 1948, now Patent 2,499,365, granted March 7, 1950, where Example 258d relates to the production of a resin from cardanol and formaldehyde and'EXamplefi-b describes production of the oxyethylated deriva tive thereof. The same procedure may be employed to produce a similar resin from chlorinated cardanol and formaldehyde, and the oxyalkylated derivative thereof, respectively. 1

A chlorinated phenol, like para-chlorophenol, may be oxyalkylated to produce a chlorine-containing, acylation susceptible product which is usable as a reactant here. If desired,"p=chlorophenol, for example, may be converted into a resinby reaction with an aldehyde, 'and said chlorine-containing phenol-aldehyde resin -may be oxalkylated to produce a reactant suitable for the present purpose. See Examp1e203a of our co-pending application, Serial No. 8,722, filed February 16,1948, for details of preparing such a resin. 7 1

Epichlorohydrin is a useful tool for introducing the chlorine atom into molecules which originally contain a reactive hydrogen atom orother reactiveelement capable of reacting with such. epiand are not described here.

Where an alkylene oxide like ethylene oxide .is employed to produce an acylation-susceptible de rivative of a chlorine-containing material, it is often desirable to employ stanm'c chloride as a catalyst in the reaction, rather than the other wise more commonly employed alkaline catalysts, like caustic soda. The reason is that such alka- Such reactions are well j-k'nov'vli line catalysts tend to de-chlorinate the halogenated reactant under the conditions which maintain during oxyalkylation, andthis elimi'f nates or destroys the catalyst.

Ethylene chlorohydrin and glycerin chlorohydrin are additional examples of usable chlofine-containing acylation susceptible reactants.

Sulfur-containing acylation-susceptible mate' f rials include Vultac, a line of resinous products of Sharples Chemicals, Inc., Philadelphia. This is the trade-mark of a number of sulfur-containing resinous materials, stated by the manufac-' turer to have the following generic structural formula:

and to contain differing amounts of sulfur,-

{Ihese products, alkylphenol sulfides, may here;

. Serial No. 8,722, filed February 16, 1948, wherein Vultac resins are referred to; and to Example 64b of said co-pending application, wherein the oxyethylation of such Vultac resin is recited;

mideformaldehyde resin manufactured by'Mon santo Chemical Company, St. Louis. Such sulfurcontaining material is referred to in Example 363d. of our co-pending application, Serial No. 8,722, filed February 16, 1948; and its oxyethylation is described in Example 77b of said co-pending application. The oxyalkylated derivatives of said Santolite MS are usable acylation-susceptible reactants here. The Santolite MS, before 'oxyalkylation, is not particularly suitable for the present purpose, because of the relative inactivity of the NH group.

Other examples of acceptable sulfur-containing reactants of the present type are to be found in U. S. Patent, No. 2,353,694, dated July 18, 194.4, to De Groote and Keiser; and in U. S. Patent No. 2,345,121, dated March 28, 1944, to Hentrich and Kirst-ahler. Thiourea-formaldehyde resins may be oxyalkylated; and such oxyalkylatedderive.

tives may be employed for the present purpose,

Sharples Chemicals, Inc., Philadelphia, also offers a polyethyleneglycol tertiary-dodecyl thio: ether under'the trade-mark Nonic 218.which an acceptable sulfur-containing reactantbf the present type, and which is made from dodecyl thioether by oxyethylation. Other oxyalkylated ceptible reactant may contain both sulfur and mercaptans immediately come to mind fasflob vious equivalents of such' product, for thep'res ent use.

It is to be understood that the acylationesusw 'achievedin a matter'of minutes.

still in xylene solution, is removed from the autoplication Serial No. 137,293.

following examples are given.

Example 1431) oxyethylated p-chlorophenol is prepared by reacting the phenol, 123 grams, with ethylene ox- .id'e, 88 .grams, in an autoclave of the kind fully described above, at a temperature of approxi- ,w

mately, 170 C.,- using 100 grams of xylene as a solvent, and 2 grams of stannic chloride to catalyze the reaction. Oxyethylation is readily The product,

clave, transferred to a glass resin pot, also adequately described above, and esterified with the carboxyl-containing resin of Example 7a of ap- Esterification is achieved by stirring and refluxing 154 grams of the solution containing about 50 grams xylene and approximately 109 grams of oxyethylated phenol so prepared, 425 grams of the amylphenolsalicylic acid-formaldehyde resin of said Example 7a, referred to, and 300 grams more of xylene for" 4 hours in the presence of 2 grams paratoluene sulfonic acid, and distilling off water of esterification. Approximately the theoretical quantity, 0.5 mole, of water was so recovered.

The product is a chlorine-containing acylation product or intermediate, usable for the preparation of oxyalkylated derivatives thereof for the present purpose.

Example 144D Instead-of oxyalkylating p-chlorophenol as in Example 143?) just above, prepare a phenol-aldehyde resin from 128 grams of the phenol and 81 grams of 37% formaldehyde, employing conventional resinification procedure. Such resin,

as prepared, contained 100 grams of xylene added nic chloride (for oxyethylation catalyst). Ethyl- .ene oxide, 88 grams, is then introduced into this resin solution, maximum temperature being about 165 C., and absorption of the ethylene oxide being accomplished in 15 minutes. Approximately 225 grams of the oxyethylated chlorophenyI-formaldehyd'e resin so prepared, in solution in 100 grams xylene, was added to 840 grams of the butylphenol-salicylic acid-formaldehyde resin of Example 9a of application Serial No. 137,293; and 300 grams more xylene were added. The mixture was placed in a conventional glass resin pot, already described, and refluxed with stirring for 5 hours, in the presence of 3 grams p-toluene sulfonic acid. At the end of this time 18 grams of water of reaction, ap-

26 proximately theoretical in amount, had distilled off. The product was a chlorine-containing, acylation product intermediate.

Example 145b Cardanol is chlorinated using the procedure recited in Example 5 of U. S. PatentpNo. 2,368,709, dated February 6, 1945, to Harvey, until approximately 2 moles of chlorine have been absorbed by each mole of cardanol. The chlorinated cardanol, 500 grams, was mixed with 1 13 grams 37% formaldehyde, 400 grams xylene, 3 grams concentrated HCl, and 1.5 grams alkylated aromaticsulfonic acid sodium salt, in a glass resin pot, and refluxed 3.5 hours, after which water of reaction was distilled ofi, the volume being about 25' ml.'

A portion of the xylene solution of the resin so formed, adjusted to contain xylene solvent, was introduced into the autoclave already described, a total of 820 grams of such solution containing 410 grams of resin, being usedfand 5 grams of stannic chloride were added as catalyst. Subsequently, ethylene oxide, 585 grams, was added in six portions, each of the first five being grams, and the sixth, grams, The additions were absorbed quite readily, the temperatures usually staying below about 160 C., and addition being achieved in a matter of about "30 minutes in each case. The product is a chlorinecontaining acylation-susceptible reactant, usable here.

The oxyethylated resin, so produced from chlorinated cardanol-formaldehyde resin, was reacted with the carboxyl-containing phenol-aldehyde resin of Example 7a of application SerialNo. 137,293. Into a glass resin pot were introduced 350 grams of the cardanol derivative 'and '395 grams of the butylphenol-salicylic acid-formaldehyde resin, 7 grams p-toluene sulfonic acid, and 500 grams xylene. After stirring with reflux for 6 hours, water of reaction was distilled, its volume being about 18 ml. The product isachlorine-co'n'taining acylation product.

Example 14Gb 40 grams of sodium methylate and 2,000 grams xylene. Ethylene oxide, 4,000 grams, was introduced into the autoclave in four lots of 1,000

" grams each. The time required for absorption of the first lot was 14' hours, at 160 C. The second lot was absorbed in the same timer The third lot was absorbed in5 hours, at 162 C.; and

- the carboxyl-containing resin,

the fourth lot was absorbed in-4 hours, at C. The product was a sulfur-containing acylationsusceptible reactant, usable here.

It was reacted with the carboxyl-containing resin of Example 7a of application Serial No. 137,293, using 400 grams of it and 500 grams of in 300 grams xylene. The mixture was stirred and refluxed in a glass resin pot for 6 hours, in the presence of 3 grams paratoluene sulfonic acid, the water of reaction being distilled. About 7 grams of water were so recovered. The product is a sulfur-containing, acylation product, suitable for later use here.

Example 147 b Santolite MS, a sulfonamide-aldehyde res'in manufactured by Monsanto Chemical Company,

perature of about 150 C., the pressure reaching 95 p. s. i. No solvent is required here, since the resin is soluble in propylene oxide. approximately 762 grams of ethylene oxide were Thereafter,

introduced in 12 portions, as follows: 44 grams in, 4 hours, maximumtemperature 150C; 57

sulfur-containing acylation-susceptible material, .was then reacted with the carboxyl-containing phenol-aldehyde resin of Example 9a of application Serial No. 137,293. In this reaction, 1230 grams of the oxyalkylated Santolite MS just prepared are mixed with 786 grams of the butylphenol-salicylic acid-formaldehyde resin or said Exp.-toluene sulfonic acid. The mixture was stirred under reflux for 8 hours, water of reaction being distilled. The product is the desired acylated intermediate. In the preparation of acylated intermediate from sulfuror chlorine-containing acylationsusceptible reactants and carboxyl-containing phenol-ald hvde resins we prefer that said acvlation-susceptible reactants have a molecular Weight not exceeding 25,000.

' OXYALKYLATION We have prepared intermediates of the kind described above on a scale varying from a few hundred grams or less in the laboratory, to hundreds of nounds'on a plant scale. The same applies in the pre aration of the oxyalkylated compounds with which this part of the specification is concerned. In preparing a large number of examples we have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. More specific reference will be made to treatment with clycide, subse uently in the text. The oxynropylation step is. of course, the same as the oxyethylation step insofar that two low bo lin li uids are handled in each instance.

' What imme iately follows refers to oxvethylation and it is under tood that oxypropylation can be han led conveniently in exactly the same manner.

The oxvethylation procedure employed in the preparation of derivatives of the preceding intermediates has been uniformly the same, parample 9a, 1,000 gramsof xylene, and 20 grams of ticnlarly in li ht of the fact that a continuous operating procedure was employed. In this particular procedure the autoclave was a conventional autoclave, made of stainless steel and having a capacity of approximately one gallon, and a working pressure of 1,000 pounds gauge pressure. The autoclave was e uipped with the conventional devices and openings, such as the variable stirrer initial reactants; at least one connection for con- 28 ducting the incoming alkylene oxide, such as ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave, such as 'a cooling jacket and, preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating with steam or cooling with water, and further equipped with electrical heating devices. Such autoclaves are, of course, in essence small-scale replicas of the usual conventional autoclaves used in, oxyalkylation procedures.

Continuous operation, or substantially continuous operation, is achieved'bythe use of a separate container to-hold the alkylene oxide being.

employed, particularly ethylene oxide. The container consists essentiallyof alaboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. equipped, also, with an inlet for charging, and an outlet tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use and the connection between the bomb and the autoclave were flexible-stainless hose or tubingso that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any otherusual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxyethylations become uniform in that the re- I action temperature could be held within a few degrees of any selected point in this particular ran e. In the early sta es where the concentration of catalyst is high the temperature was generally set for around C. or thereabouts.

Subsequently temperatures up to C. or higher may be required. It will be noted by examination of subsequent examples that this temperature range was satisfactory. In any case, where the reaction goes more slowly a higher temperature may be used, for instance, 165 C. to C.,

and if need be C. to C. Incidentally,

oxyprooylation takes place more slowly than oxyethylation as a rule and for this reason we have used a temperature of approximately 160 C. to 165 0., as being particularly desirable for initial oxypropylation, and have stayed within the range of 165 C. to 185 0., almost invariably during oxypropylation. The ethylene oxide was forced in by means of nitrogen pressure as rapidly as it was absorbed as indicated by the pressure gauge on the autoclave. In case the reaction slowed up the temperature was raised so as to speed up the reaction somewhat by use of extreme heat. If need be, cooling water was employed to control the temperature.

As previously pointed out in the case of oxy-'- propylation as differentiated from oxyethylation,

there was a tendency for the reaction to slow up as the temperature dropped much below the selected point of reaction, for instance, 170 C. In this instance the technique employed was the same as before, that is, either cooling water was cut down or steam was employed, or the addition of propylene oxide speeded up, or electric heat us d. in a dition to thesteam, in order that the This. bomb was reaction proceeded at, or near, the selected temperatures to be maintained.

Inversely, if the reaction proceeded'too fast regardless of the particular alkylene oxide, the amount of reactant being added, such as ethylene axiagw'as cut down or electrical heat was cut oil, or steam was reduced, or if need be, cooling water was run through both the jacket and the cooling coil. All these operations, of course, are dependent on the required number of conventional gauges, check valves, etc., and the entire equipment, as has been pointed out, is conventional, and, as far as'we are aware, can be furnished by at least two firms who specialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requires extreme caution. This is particularly true on any scale other than small laboratory or semi-pilot plant operations. Purely from the standpoint of safety in the handling of glycide, attention is directed to the following: (a)

If prepared from glycerol monochlorohydrin, this separable glass resin pot as described in the copending a plication of Melvin De Groote and Bernhard Keiser, Serial No. 8.722, filed February 16, 1948, now Patent 2.4 9.365. granted March 7, 1950, and offered for sale by numerous laboratory sup ly houses. If such arran ement is u ed to prepare laboratory scale duplications, then care should be taken that the heating mantle can be removed rapidly so as to allow for cooling; or better still, through an added opening at the top the glass resin pot or comparable vessel should be equipped with a stainless steel cooling coil so that the pot can be cooled more rapidly than by mere removal of mantle. If a stainless steel coil is introduced it means that the conventional stirrer of the paddle type is changed into the centrifugal type which causes the fluid or reactants to mix due to swirling action in the center of the pot. Still better, is the use of a laboratory autoclave 'of the kind previously described in this part; but in' any event, when the initial amount of glycide is added to a suitable reactant, the speed of reaction should be controlled by the usual factors, such as (a) the addition of glycide; (b) the elimination of external heat, and use of cooling coil so there is no undue rise in temperature. All the foregoing is merely conventional but is included due to the hazard in handling glycide.

Example .col., and the amvl-phenol-salicylic-acid-formale dehyde resin of Example 7a of application Serial No. 137,298 were reacted to producean ester 1514 grams of solvent (xylene).

which is the acylated product or intermediate employed in the present example), dissolved in 8 grams of sodium methylate were added. The autoclave was sealed, swept with nitrogen gas, stirring started immediately and the temperature allowed to rise to l52.5 C. At this point addition of ethylene oxide was started. It was added continuously at such speed that it was absorbed by the reaction as rapidly as added. The amount of ethylene oxide added was 254 grams. The time required to add the ethylene oxide was less than 10 minutes, as a matter of fact, only about 5 minutes were required. During this short reaction period the temperature rose rapidly to '180" C. The temperature was held at a maximum of 180 C., by using cooling water through the coils when required, or otherwise applying heat when needed. The maximum pressure during this short reaction period was 215 pounds. The product at the end of this reaction was somewhat emulsifiable but not clearly soluble.

The oxyethylation product produced as just described was subjected to further oxyethylation in the same manner, employing 326 grams of the solvent-free product of the first stage of oxyethylation, 326 grams of xylene solvent, no additional catalyst, and 1'73 grams more of ethylene oxide. In 5 minutes after introduction of the additional ethylene oxide, absorption thereof was substantially complete. The maximum temperature in this second stage of oxyalkylation was 170 C. and the maximum pressure observed was 180 p. s. i. The product was readily watersoluble, i. e.. readily water-dispersible.

Referring back to Example 10 just above, it will be noted that a total of 427 grams of ethylene oxide was employed in the two stages of the reaction there conducted. When glycide was substituted for ethylene oxide in the example, only 500 grams of glycide were employed in spite of its molecular weight (about two-thirds reater than that of ethylene oxide). The glycide was charged into the upper reservoir vessel which had been flushed out previously with nitrogen and I was the equivalent of a separatory funnel.

- 110 C. to 130 C. The addition was continuous '-within the limitations and all the glycide was added in less than 4% hours.

This reaction took place at atmospheric pressure with simply a small stream of nitrogen passing into the autoclave at the very top and passing out through the open condenser so as to avoid any entrance of air. The final product was distinctly water-soluble.

The following table illustrates a number of other oxvalkylation derivatives of acylation or intermediate products described above all prepared in the manner outlined in Example 10 immediately preceding. .The table identifies the products by example number, shows the amount of intermediate products used, the amount of solvent, the amount of catalyst, the amount of al- 3 kylene oxide, the time required, the maximum Amt Solvent Sod. Ratio Taken, EtO Temp. Max. P Gms. Present Methylate Added, Tune Mair, Pres, lbs. E10? Solubility in Water No. tive N o. (Solvent ms. dde Gms (hrs) er S in Phenolic Free) (Xylene) Gms. P Hydroxyl I 1010. 1000 191. 5 118. 5 77 M2 150 Emulsifiablc. 1020-- 1010 168 74 67 M2 150 Water Soluble. 1030- 651) 261 412 7 235 M2 180 Emulsifiable. 1040.- 1030 301 251 188 M2 185 Do. 1050- 1040 272 139 M 150 Soluble. 1060- 66b 288 426 256 M2 180 Emulsifiable. 1070.. 1060 306 238 200 M2 190 Soluble. 1080- 6717 192 447 192 M 2 200 Emulsifiable. 1090.- 1080 174 203 97 M2 180 D0. 1100-. 1090 160 30 M 160 Soluble. 1110- L 68b 262 368 7 262 M 2 190 Emulsifiable. 1120.. 1110 306 214 173 M2 185 Soluble. 1130. 69b 280 384 8 265 M 180 Emulsifiable. 1140.. 1130 359 254 192 M2 180 Do. 1150-. 1140 342 158 57 M2 160 Soluble. 1160- 70b 187 398 8 185 M 180 Emulsifiable. 1170.. 1160 224 240 121 M2 170 Do. 1180-. 1170 218 151 58 Mg 160 Soluble. 1190.. 716 256 396 8 255 M 180 Emulsifiable. 1200.- 1190 349 271 180 M2 170 Do. 1210.- 1200 339. 172 60 M --160 Soluble. 1220- 72!) 265 537 8 264 $6 180 Emulsifiable. 1230- 1220 307 307- 160 M 2 180 Soluble. 1240- 730 201 402 8 201 M 180 Emulsifiable. a 1240 264 263 132 M 2 170 Soluble. 1260- 74!) 242 484 244 ,6 180 Emulsifiable. 1270. 1260 286 283 149 M 2 160 Soluble. 1280- 751) 272 544 284 M 2 180 Emulsifiable. 1290- 1280 375 366 177 M 2 180 Soluble. 1300- 76b 231 462 241 M2 160 Emulsifiable. l 1310- 1300 284 279 131 M 2 180 Soluble. 1320- 770 263 526 260 M2 170 Emulsifiable.

D a Amt. Tak- Solvent $38 Eto Tem Max. E 1v en Gms. Present Time Press. Solubility in x. o. tive ylate Added Max.

N0 (Slolveiit (xGrlus. Added (Gms (hrs) 00 lbs. pe11; water ree y ene (Gum) sq. 111C 9412 257 254 M 2 180 215 Emulsifiable.

a 22 5s a s e... 95 270 2 1 0 mu S: a e. 1350 358 179 M 2 170 190 Soluble.

960 252 282 16 195 200 Emulsiflable. 343 3 i2 138 138 S i s b1 97 255 5 mu si a e. 1390 313 140 $6 165 160 Soluble.

985 271 281 M 195 240 Emulsifiable. 1410 289 M2 180 190 D0. 142:: 251 35 M2 70 Soluble.-

991) 222 314 M2 200 240 Do. 1505 260 260 M 190 245 Emulsifiable. 1450 320 160 M2 190 Soluble. I 1015 298 298 M 195 230 Emulsifiable. 1470 396 198 H 2 170 210 Soluble. 1025 282 282 M 195 230 Emulsifiable. 1496 364 182 M2 190 200 Soluble. 103!) 252 265 M3 220 Emulsifiable. 1510 263 147 M 180 200 Soluble. 1041) 275 295 M 180 225 Emulsifiable. 1530 316 170 M; 185 Soluble. 1050 419 419 M, 190 240 Emulslfiable. 1550 588 299 $6 190 230 D0. 1560 582 217 $6 175 190 1 This product at this stage was emulsifiable but further oxyethylation did not seem particularly to increase solubility. For the present process the procedure was stopped at this particular point.

Example 1580 The reaction vessel employed was a stainless steel autoclave equipped with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., which are conventional for this type of apparatus. The capacity was approximately 3.5 liters. The stirrer was operated at a speed of approximately 250 R. P. M. There was charged into this autoclave 216 grams of the acylated intermediate, prepared in Example 1066 above, dissolved in 392 grams of xylene as solvent. Then 8 grams of sodium methylate catalyst were added. The autoclave was closed, then swept with nitrogen gas. Stirring was started and the temperature raised to about 150 C. At this point, addition of ethylene oxide was begun; and addition was thereafter continuous at such speed that absorption was substantially immediately achieved. The amount of ethylene oxide added was 216 grams, and the addition time was 0.5

hour. The maximum temperature during addition was 170 0., temperature being controlled by circulating cooling water through the autoclave jacket or applying steam for heating, as required. The maximum pressure observed during the reaction was 220 p. s. i. The oxyethylated product so obtained was emulsifiable in water in the presence of the xylene solvent.

Exampl 1590 35 (really, water dispersible") It was not further reacted with the alkylene oxide.

Various other oxyalkylation procedures were employed on the acylated intermediates previously prepared, all in the manner just set out above. These are shown in the following table. In it, the nature of the acylation product or intermediate, the amount of it employed, the amount of xylene employed as solvent, of sodium methylate catalyst employed, if any, the amount of ethylene oxide used, the reaction time, maximum temperature and pressure observed, and dispersibility of the oxyethylated product in water, ar all set forth.

- Max. Max Am T m ea. taxes? a 3.3 e 1 mm 1586... 10617 216 216 0.5 170 220 Emulsifiable. 1596.-. 1586 234 113 0. 08 180 220 Soluble. 1606 1070 180 180 0. 16 180 220 Emulsifiable. 1616.. 1606 164 82 0. 08 170 150 oluble. 1626. 1030 198 212 0. 08 180 250 Emulsifiable. 1636.. 1626 212 108 0. 16 170 220 Soluble. 1646.-. 1096 155 155 0. 180 200 Emulslfiable. 1656... 1646 161 86 0. 16 160 150 Soluble. 1666... 1100 175 190 0.25 180 200 Emulsifiable. 1676... 1666 162 86 0. 16 160 150 Soluble. 1686... 1110 196 210 0. 25 180 220 Emulsifiable. 1696... 1686 204 107 0. 16 160 150 Soluble. 1706... 1120 207 211 0. 25 180 220 Emulsifiable. 1716... 1706 220 112 O. 16 160 150 Soluble. 1726--. 1130 250 235 0. 16 170 220 Emulsifiable. 1736... 1726 259 160 0. 08 180 200 Soluble. 1746... 114b 229 215 0. 16 175 220 Emulsifiable. 1756... 1746 288 180 0.08 185 210 Soluble. 1766... 11517 223 215 0. 16 180 210 Emulsifiable. 1776... 1766 295 165 0.08 185 190 Soluble. 1786.-. 1160 196 205 0.08 180 210 Emulsifi'able. 1796... 1786 227 140 0. 08 160 150 Soluble. 1806. 1176 194 200 0.08 165 190 Emulsifiable. 1816 1806 215 140 0. 08 160 170 Soluble. 1826... 1180 202 200 0. 08 165 195 Emulsifiable. 1836... 1826 213 r 0.08 150 Soluble. 1846... 1196 196 205 0. 08 175 200 Emulsifiable. 1856-.. 1846 231 130 0. 08 160 160 Soluble. 1866-.. 1200 208 208 0. 25 175 195' Emulsiflable. 1876... 1866 248 165 0. 08 185 170 Soluble. 1886.. 1210 284 291 0. 25 175 210 Emulsifiable 1896. 1886 336 175 0. 08 185 190 o. 1906-.. 1896 333 60 0.08 160 110 Soluble. 1916-. 1225 304 304 0. 25 190 230 Emulsifiable. 1926... 1916 '333 175 0. 16 180 210 Do. 1936... 1926 255 75 0. 16 160 Soluble. 1946.. 1235 200 200 0. 33 175 190 Emulsifiable. 1956... 1946 226 145 0. 16 175 185 Soluble. 1966... 124b 188 188 0. 08 165 210 Emulsifiable. 1976... 1966 201 117 0. 08 180 170 oluble. 1986... 1250 208 208 0. 25 175 200 Emulsifiable. 1996... 1986 282 0. 16 175 185 Soluble. 2006... 126b 436 436 0. 33 170 210 Emulsifieble. 2016... 2006 386 205 0. 08 160 205 Soluble. 2026... 1276 386 386 0. 16 180 240 Emulsifiable. 2036... 2026 407 215 0.08 170 200 Do. 2046... 2036 326 215 0. 33 170 200 Soluble. 2056... 1281; 286 286 0. 08 175 200 Emulsifiable. 2066.. 2056 366 205 0.08 185 210 Soluble. 2076... 1296 264 264 0. 16 v 200 Emulsifiable. 2086.-. 2076 271 145 0. 08 175 190 Soluble, 2096... 130b 179 189 0. 16 200 Emulsifiable. 2106.. 2096 204 120 0. O8 170 160 Soluble. 2116... 131!) '341 341 0. 08, 190 220 Emulsifiable. 7 2126... 2116 319 170 0.08 185 200 7 Do. 2136. 2126 253 135 0. 08 170 190 Soluble. 2146... 1320 269 269 0. 25 180 190 Emulsifiable. 2156. 2146 306 165 0. 08 170 180 oluble. 2166... 1330 239 239 0.08 170 Emulsifiable. 2176... 2166- 275 155 0. 08 175 oluble. 2186.. 1346 31-8 340 0. 08 195 210 Emulsifiable. 2196... 2186 401 215 0.08 195 210 Soluble. 2206.. 1350 299 305 0. 25 165 220 Emulsifiab'le. 2216... 2206 376 196 0.08 210 Soluble. 2226... 1360 272" 272 0. 08 175 210 Emulsl'fia'ble. 2236.. 2226 308 150 0. 08 175 180 Soluble. 2246... 1370 303 303 0. 16 175 200 Emus'llfiable. 2256.-. 2246 368 200 0. 08 210 D0. 2266.. .2256 283 237 O. 16 160 180 Soluble. 2276. 1380 321 334 O. 16 210 Emulsifiable. 2286... 2276 424 220 .0. 08 190 220 Do. 2296.. 2286 368 260 0. 16 170 180 Soluble. 2306.-. 13% 324 324 0. 16 190 230 Emulsifiabl'e. 2316.. 2306 362 '200 0. 08 .185 190 Soluble. 2326-.- 1400 334 348 0. 16 r 190 220 Emulsifiable. 2336... 2326 362 196 0. 08 180 190 oluble. 2346..- 14117 327 340 0. 16 195 210 Emulsifiable. 2356..- 2346 398 209 0. 08 190 220 Soluble. 2366..- 1421) 213 213 0. 08 195 210 Emulsifiable. 2376.-- 2366 275 150 0.08 .180 180 Soluble.

' nic chloride, grams.

'3' Example 2390 Use the acylated intermediate of Example 145D above, 735 grams; xylene, 500 grams: stannic chloride, 7 grams. Place in the oxyalkylation, autoclave and introduce ethylene oxide continuously until a total of 440 grams has been absorbed. The time required is about 5 hours, the maximum temperature, above 165 C. Then, introduce a total-of 116 grams propylene oxide into the mass,

.by disconnecting the ethylene oxide supply and attaching the propylene oxide supply. Absorption was somewhat slower, but was accomplished in 2 hours. Thereafter, introduce an additional 110 grams ethylene oxide, as before. The time required was about 0.5 hour. The final product showed water-dispersibility.

Example 241 c The acylated intermediate of Example 14Gb above was used, 500 grams. Into the autoclave were also introduced 500 grams xylene and 5 grams stannic chloride. Ethylene oxide, 440 gra ns, was then introduced in continuous fashion, as above. Absorption was complete in '7 hours, maximum temperature being 170 C. The

-' final product was water-dispersible.

Example 2420 Use the 'acylated intermediate of Example 14% above, 500 grams; xylene, 500 grams; and stan- Introduce this mixture into the autoclave and then feed ethylene oxide continuously until a total of 550 grams have been absorbed. The time required was about 6 hours, and the maximum temperature attained was 175 C. The product was water-dispersible.

In addition to ethylene oxide, propylene oxide, glycide, orv mixtures of the two, or all three of these oxides, one can use also methyl glycide and butylene oxide. Butylene oxide, if employed at all, should be used in combination with ethylene oxide, glycide or methyl glycide. The most desirable combination is, of course, one in which the oxyalkylated derivative shows marked surface-activity, which can be readily detected by an emulsification test as explained below.

The alpha-beta olefin oxides, employed to produce, from the acylated intermediates, oxyalkylated derivatives which are distinctly hydrophile in nature, as shown by the fact that they are self-emulsifiable or self-dispersible, mis- "cible, or soluble in water, or have emulsifying properties, are characterized by the fact that .they contain not over 8 carbon atoms and are selected from the class consisting of ethylene .oxide, propylene oxide, butylene oxide, glycide, and methyl glycide. Glycide may, of course, be considered :as a hydroxypropylene oxide and methyl glycide as a hydroxybutylene oxide. In any event, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of, or substituted, ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glyclde, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, is propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the intermediate composition is such as to make incorporation of the desired property practical. In other case, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the .acylation product molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product. The reverse procedure may likewise be employed. Used alone, these two reagents may in some cases fail to produce sufiiciently hydrophil derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is more effective than propylene oxide, and propylene oxide is more effective than butylene oxide. Hydroxypropylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxybutylene oxide (methyl glycide) is more effective than butylene oxide.

Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. ,Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care, as previously noted.

, As has been previously pointed out, the oxyalkylation of intermediates of the kind from which the products used in practicing the process of the present invention are prepared is advantageously catalyzed by the presence of an alkali, except in certain cases, as where the product is a chlorinated product, in which case, to minimize dechlorination, a catalyst, such as stannic chloride (see Examples 2380-2420) is advantageously used... Useful alkaline catalysts include soaps. sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e.,,from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of an intermediate in determining the amount of alkaline catalyst to be added in its oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resinification or intermediate reaction, presumably after being onvert'ed into asulforiic acid; it-may be riecessary and is usually advantageous to add'a-n amount of alkali equal stoichiometricall-y to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct/theoxyethyla'tion of the intermediate in presence ofan inert solvent such as xylene, cymene, decalin, ethyleneg'ly'col diethylether, diethyleneglycoldiethylether, for the like, although with many products, the oxyalkylation proceeds satisfactorily without a;solvent. Since 'x'ylene is cheap and'may be 'permittedto be present in the finalproduct whenused asa de- I niulsifier, it is our preference touse xylene,

Considerable of-what is saidiimmediatelyhere inafter is concerned with the ability to vary-the hydrophile properties of thefcompounds used in the process from minimumhydrophileproperties to maximum hydrophile properties. Even more remarkable, and-equally difficult to explain,

are the versatility and utility of these compounds asonegoes from hydrophile property to ultimate maximum hydrophile property, "For instance, minimum 'hydro'phile property may usually be described roughlyas the point where two ethyleneoxy ra'dicalsor moderately in excess thereof are introduced per phenolic I hydroxyl. Such "minimum hydrophile property or sub-surface-activity or "minimum surface-activity means at he product. w jatgleast emu sif g prop,-

erties orself-disp'ersion in 'cold or even in warm distilled water (15? to 40 C.) in concentration, of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water; and may even be very insoluble in boiling water. Moderately high temperatures aidfin reducing the viscosity of the solute under examination,"

Sometimesif one continues ,to shake a hot solution, even though "cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Suehselfedispersion tests are conducted in the absence of an insoluble solvent. 7

When the hydrophile-hydrophobe balance is above the indicated minimum but insuflicient to give a sol as described immediately preceding, then, in that event hydrophile properties are in"- dicated by the fact that one can produce an-emulsion by having present 10% to 50% of an inert solvent such as xylene.

-50 to 90 parts by Weight of oxyalkylated derivatives and '50 to 10 parts by weight of xylene, mix such solution with one, two or three times its volume of distilled water, and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. luted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not sufiicient to permit the simple sol test in water previously noted.

If the product is not readily water-soluble it may be dissolved in ethyl or methyl alcohol,

ethyleneglycol diethylether, or diethyleneglycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance 40% to 50 and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5 to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is aliquid or All that one need to do .7 is to have a xylene solution within the range of We prefer simply to use the xylene-di- 40 a liquid solution sli -erhul'sifi ablel, such sol of dispersion is referred to as at least semi-stable in the sense 'thatsols, emulsions, or dispersions prepared are relatively stable, if they remain at least fo'r'some period or time, for instance 30 minutes to twohours,"beforefshowing any marked separation. Such tests are conducted at room temperature (22? "C.). Needless to say, a testcan be m'ade ,in pres'enceofan insoluble solvent such as 5% to. 15% of xylendas noted in previous excontaining a a'lllples.v If such mixture, i. e., water-insolublesolvent, is at, least semi-stable, obviously. the. solvent-free product would be even more so, Sur'facer'activity representing an advanced 'hydrophile-hydrophobe balance can also be determined by,.the us,e,o f conventional mea's urements' hereinafter described. One outstanding characteristic: property indicating surfa'ceactivity in a material is the ability to-form a permanent foam Jinn-dilute aqueous solution, for

example, less than 0.5%, when in the higher oxy-,

alkylatedstageand to forman emulsion in, the lowera-nd intermediate stages of oxyalkylation.

Allowance must be made :for the presence of a solvent i-n-zth'e final product in relation-to the hydrophilea propertiesof the final product The principle involved in-theq-manufacture of the.

herein contemplated compounds for use ,-.as dee mulsifying agents or for other uses, is based on the conversion-of a hydrophobe or non-hydro:- -phile compound or mixture of compounds into products whichare distinctly hydrophile, at least to the extent that they have emulsifying properties or are self-emulsifying; that is, when shaken with water they produce stable or semi-stable suspensions, 'or,fin'the presence-of "a water-insoluble solvent, suchas xylene, an emulsion. Y In demulsification itissometimespreferable' to :use

a product having -markedly enhanced :hydrophile' properties over and above the initial stage of self emuls'ifiability; although we havef ound that with products of. the ty used herein, most'effie cacious results are obtained with products which do not have hydrophileproperties beyond the stage of self-dispersibility.

More highly-foxyalkylated. 'ac-ylatedproducts 7 give-colloidal solutions or sols which show typical roperties comparable to ordinary surface-active agents Such conventional surface-activity may be-measured by determining the surface tension and'theinterfacial tension against paraffin oil or thelike; At the initial and lower stages .of

oxyalkylation, surf ace-activity is-notsuitably de-l termined in this same manner but one may employ an'emulsification test. Emulsions come into 'is then mixed w-ith. l-3 volumes of 'water and .sha'kenqto producean emulsion: The iarrl'ountt of xylene isv invariablylsufiicient to-r'educe ever ua tacky,- resinousproduct to a'solutionfw-hich is readily water dispersible. The emulsionsso pm- 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING HYDROPHILE SYNTHETIC PRODUCTS, SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF THE ACYLATION PRODUCT OBTAINED BY REACTING (A) A FUSIBLE CARBOXYL-CONTAINING, XYLENESOLUBLE, WATER INSOLUBLE, LOW STAGE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A MIXTURE OF A DIFUNCTIONAL MONOHYDRIC HYDROCARBON-SUBSTITUTED PHENOL AND SALICYLIC ACID ON THE ONE HAND, AND ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND ONE FUNCTIONAL GROUP REACTIVE TOWARD BOTH COMPONENTS OF THE MIXTURE ON THE OTHER HAND; THE AMOUNT OF SALICYLIC ACID EMPLOYED IN REALTION TO THE NON-CARBOXYLATED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEAST ONE SALICYLIC ACID RADICAL PER RESIN MOLECULE AND THE AMOUNT OF NONCARBOXYLATED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEAST ONE NON-CARBOXYLATED PHENOL RADICAL PER RESIN MOLECULE; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO AND SAID PHENOL BEING OF THE FORMULA 